Gas Generant Compositions

ABSTRACT

A fuel component for an airbag inflator, dinitrosalyicylic acid and derivatives thereof, is used as a primary fuel in a gas generating composition  12.  A novel gas generating composition  12,  containing the primary fuel, and phase stabilized ammonium nitrate is also provided. The fuel component may be contained within a gas generant composition  12,  within a gas generator  10.  The gas generator  10  may be contained within a gas generating system  200  such as an airbag inflator  10  or seat belt assembly  150,  or more broadly within a vehicle occupant protection system  180.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Ser. No. 61/318,138 filed on Mar. 26, 2010 and PCT Application Serial No. PCT/US11/00560 filed Mar. 28, 2011.

TECHNICAL FIELD

The present invention relates generally to gas generating systems, and to gas generating compositions employed in gas generator devices for automotive restraint systems, for example.

BACKGROUND OF THE INVENTION

The present invention relates to gas generating compositions that upon combustion produce a relatively smaller amount of solids and a relatively abundant amount of gas. It is an ongoing challenge to reduce the amount of solids and increase the amount of gas thereby decreasing the filtration requirements for an inflator. As a result, the filter may be either reduced in size or eliminated altogether thereby reducing the weight and/or size of the inflator. Additionally, reduction of combustion solids provides relatively greater amounts of gaseous products per gram or unit of gas generating composition. Accordingly, less gas generant is required when greater mols of gas are produced per gram of gas generant. The result is typically a smaller and less expensive inflator due to reduced manufacturing complexity.

In a related challenge, when increasing the amount of gas, the effluent must be tailored to ensure that carbon monoxide or other less-than-desirable gases are attenuated. For example, when increasing the relative amounts of carbon in the gas generant, one concern is whether the gas generant might produce more carbon monoxide as a combustion product. As such, the effort to reduce solids and increase gas production upon combustion, must be balanced with combustion products that meet current effluent standards.

Another challenge is providing gas generating compositions that meet current USCAR requirements for chemical and thermal stability. Chemical stability is indicative of a propellant retaining its structural integrity over time. Dimensional stability is indicative of chemical stability, the retention of density over time for example. Components of the composition must be compatible with each other with a minimum of interaction. Therefore, chemical stability involves the mitigation of interaction of the various constituents that are included in the gas generating composition.

Thermal stability is the ability to retain structural integrity when cycled between −40 C and 107-110 C, for example. For example, the composition may be held at a temperature of −40 C for a period of time and then quickly brought to a temperature of about 107 to 110 C and held there for a period of time. Accordingly, retaining gas generant structural integrity while undergoing periodic cycling between the two temperature regimes over time is yet another challenge. Furthermore, USCAR requirements include thermal testing by holding compositions at about 107 C for about 400 hours without a decomposition of the compositions. Certain compositions containing phase stabilized ammonium nitrate, for example, oftentimes present concerns with regard to thermal stability.

Yet another concern is that the compositions must exhibit burn rates that are satisfactory with regard to use in vehicle occupant protection systems. In particular, compositions containing phase stabilized ammonium nitrate may exhibit relatively lower burn rates requiring various measures to improve the burn rate. Accordingly, the development of energetic fuels is one ongoing research emphasis whereby the less aggressive burn characteristics of preferred oxidizers such as phase stabilized ammonium nitrate are accommodated and compensated for by careful blending or combining of new and useful constituents.

In sum, it has been found that oftentimes nitrated aromatic compounds combined with ammonium nitrate or phase stabilized ammonium nitrate are not clean burning and may form large amounts of soot-like residues when combusted. Acidic nitro-aromatic compounds provide some measure of catalytic impetus to ammonium nitrate or phase stabilized ammonium nitrate compositions, particularly in view of the ignitability and sustained combustion concerns with some compositions containing ammonium nitrate (stabilized or not).

In view of these concerns, would be an improvement in the art to provide an ammonium nitrate or phase stabilized ammonium nitrate based composition that meets or exceeds the relative gas output of typical high-nitrogen fuels combined with an ammonium nitrate or phase stabilized ammonium nitrate oxidizer while yet retaining the performance of or improving upon the considerations provided above.

SUMMARY OF THE INVENTION

The above-referenced concerns are resolved by gas generators or gas generating systems containing a novel fuel constituent, 3,5-dinitrosalicylic acid (DNSA), a metallic of DNSA, a non-metallic salt of DNSA, or an adduct of DNSA with another compound that forms a hydrogen bonded complex. When combined with phase stabilized ammonium nitrate (PSAN) (stabilized, for example only, with potassium nitrate provided at 10-15% by weight of the PSAN), one or more of the present fuels result in a gas generant composition that exhibits optimum bum rates at relatively lower operating combustion pressures, and optimum thermal and chemical stability, notwithstanding the use of PSAN. Furthermore, one or more of the present compositions combust readily at relatively lower combustion pressures thereby resulting in relaxed manufacturing and structural requirements for an associated gas generator or airbag inflator. Yet further, one or more of the present compositions when combusted result in relatively greater amounts of gas and lower amounts of solids, and therefore improved effluent quality.

An optional second fuel may be selected from tetrazoles and salts thereof, triazoles and salts thereof, azoles and salts thereof, guanidines and salts thereof, guanidine derivatives, imides, amides, aliphatic carboxylic acids and salts thereof, aromatic carboxylic acids and salts thereof, nitro-aromatic carboxylic acids and salts thereof, nitrosalicylic acids and salts thereof, amines, nitrophenols, pyrazoles, imidazoles, azines, and mixtures thereof.

A primary oxidizer may be selected from metal and nonmetal nitrates, nitrites, chlorates, perchlorates, oxides, other known oxidizers and mixtures thereof.

If desired, other known constituents may also be utilized in known effective amounts.

In further accordance with the present invention, a gas generator or gas generating system, and a vehicle occupant protection system incorporating the gas generant composition are also included.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional side showing the general structure of an inflator in accordance with the present invention,

FIG. 2 is a schematic representation of an exempla vehicle occupant restraint system containing a gas generant composition in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The above-referenced concerns are resolved by gas generators or gas generating systems containing an acidic nitrated aromatic compound as a primary fuel, the primary fuel including a member selected from the group of 3,5-dinitrosalicylic acid (DNSA), a metallic salt of DNSA, a non-metallic salt of DNSA, or an adduct of DNSA with another pound that forms a hydrogen bonded complex. Examples of salts of DNSA include ammonium dinitrosalicylic acid, potassium dinitrosalicylic acid, strontium din salicylic acid, and copper dinitrosalicytic acid. Examples of adducts include an duct of DNSA and amino-triazole; of DNSA and melamine; and of DNSA and alkyl amines. When combined with phase stabilized ammonium nitrate (PSAN) (stabilized, for example only, with 10-15% by weight of the PSAN with an alkali metal salt such as potassium nitrate), one or more of the present fuels result in a gas generant composition that exhibits optimum burn rates at relatively lower operating combustion pressures, and optimum thermal and chemical stability, notwithstanding the use of PSAN. Furthermore, one or more of the present compositions combust readily at relatively lower combustion pressures thereby resulting in relaxed manufacturing and structural requirements for an associated gas generator or airbag inflator. Yet further, one or more of the present compositions when combusted result in relatively greater amounts of gas and lower amounts of solids and therefore improved effluent quality. When used without other fuels, the primary fuel may be provided at 20 wt % to 80 wt %, 25 wt % to 75 wt %, or at 40 wt % to 60 wt % of the total composition. All other percentages hereinafter make reference to weight percents of the total composition.

Optional secondary fuels may be selected from tetrazoles such as 5-aminotetrazole; metal salts of azoles such as potassium 5-aminotetrazole; nonmetal salts of azoles such as diammomium salt of 5,5′bis-1H-tetrazole: nitrate salts of azoles such as 5-aminotetrazole; nitramine derivatives of azoles such as 5-aminotetrazole; metal salts of nitramine derivatives of azoles such as potassium 5-aminotetrazole; nonmetal salts of nitramine derivatives of azoles such as monoammonium 5-aminotetrazole; salts of guanidines such as guanidine nitrate; nitro derivatives of guanidines such as nitroguanidine; azoamides such as azodicarbonamide; nitrate salts of azoamides such as azodicarbonamidine dinitrate; aliphatic carboxylic acids such as fumaric acid, tartaric acid, and succinic acid, and metal and nonmetal salts thereof; aromatic carboxylic acids such as benzoic acid, phtalic acid and isophthalic acid, and metal and nonmetal salts thereof; nitro-aromatic carboxylic acids such as nitrobenzoic acid, dinitrobenzoic acid, nitroisophthalic acid, and 4-hydroxydinitobenzoic acid, and metal and nonmetal salts thereof; mono-nitrosalicylic acids such as 3-nitrosalicylic acid and 5-nitrosalicylic acid and metal and nonmetal salts thereof; amines such as melamine; amides such as oxamide; imides; nitrophenols such as nitrophenol, 2,4-dinitrophenol, and picric acid, and metal and nonmetal salts thereof; triazoles such as 3-nitrotriazole and nitrotriazolone (NTO); pyrazoles; imidazoles; azines; and mixtures thereof The secondary fuel can be used within this system as co-fuels to the primary fuel. U.S. Pat. Nos. 5,872,329 and 6,210,505 describes the use of these and provision of these fuels and are both herein incorporated by reference in their entirety. When used the secondary fuel in combination with the primary fuel may constitute about 10-90 wt % of the gas generant composition. Also, when the secondary fuel is employed, the primary fuel may be provided from 5 wt % to 80 wt % of the total composition. By itself, the optional secondary fuel may constitute 0.1-45 wt % when used, and more preferably about 3-30 wt % when used.

An oxidizer is selected from metal and nonmetal nitrates, nitrites, chlorates, perchlorates, oxides, hydroxides, other known oxidizers, and mixtures thereof. The preferred primary oxidizer is selected from ammonium nitrate and phase stabilized ammonium nitrate, and most preferably phase stabilized ammonium nitrate. The primary oxidizer may be provided at 20 wt % to 80 wt %, and more preferably at 50 wt % to 80 wt % of the total composition. All other percentages hereinafter make reference to weight percents of the total composition.

A secondary oxidizer component is optionally selected from at least one exemplary oxidizer selected from basic metal nitrates, and, metal and nonmetal nitrates, chlorates, perchlorates nitrites, and oxides, including such oxidizers as basic copper (II) nitrate, strontium nitrate, potassium nitrite, iron oxide, and copper oxide. Metal-containing oxidizers include those formed from alkali, alkaline earth, and transition metal oxidizers. Other oxidizers as recognized by one of ordinary skill in the art may also be employed. The secondary oxidizer is generally provided at about 0-50 wt % of the gas generant composition.

If desired, other known constituents may also be utilized in known effective amounts.

Metal and non-metal carbonates such as di-potassium carbonate and ammonium carbonate may also be employed with an oxidizer such as ammonium nitrate.

Processing aids such as fumed silica, boron nitride, and graphite may also be employed. Accordingly, the gas generant may be safely compressed into tablets, or slugged and then granulated. The processing aid is generally provided at about 0-15 wt %, and more preferably at about 0-5 wt %.

Slag formers may also be provided and are selected from silicon compounds such as elemental silicon; silicon dioxide; silicones such as polydimethylsiloxane; silicates such as potassium silicates; natural minerals such as talc and clay, and other known slag formers. The slag former is typically provided at about 0-10 wt %, and more preferably at about 0-5 wt %.

The compositions of the present invention may be formed from constituents as provided by known suppliers such as Aldrich or Fisher Chemical companies. The compositions may be provided in granulated form and dry-mixed and compacted in a known manner, or, wet-mixed and formulated as described in the examples, or otherwise mixed as known in the art. The compositions may be employed in gas generators typically found in airbag devices or occupant protection systems, or in safety belt devices, or in gas generating systems such as a vehicle occupant protection system, all manufactured as known in the art, or as appreciated by one of ordinary skill.

EXAMPLES Example 1

Wet Mix Method Including A Secondary Fuel

A composition was made by providing a jacketed mixing vessel containing about two liters of ethanol. To this solution, about 753 grams of dinitrosalicylic acid (DNSA) was added while continuously stilling. The solution was then heated slowly to about 105 C over about thirty minutes and maintained throughout the remaining process. Once the DNSA was completely dissolved, about 4352 grams of ammonium nitrate, about 122 grams of potassium nitrate, about 227 grams of potassium carbonate (whereby potassium nitrate and potassium carbonate taken together provide a potassium source for phase stabilization of the ammonium nitrate), about 595 grams of diammonium bitetrazole, and one liter of water are added together into the vessel, while continuously and mechanically stirring. A bright yellow precipitate forms immediately in a viscous, paint-like consistency. After about one hour, the mix forms crumbly solids. The mixing and heating is continued until the desired dryness is obtained. If desired, the mix may be formed into desired shapes such as pellets or tablets and then dried to a desired moisture content, in an oven for example.

Example 2

Wet Mix Method

A composition was made by providing a jacketed mixing vessel containing about two liters of water or ethanol, or any other suitable solvent such as ethers or alcohols. To this solution, an approximate stoichiometric amount of dinitrosalicylic acid (DNSA) or a metal or nonmetal salt of DNSA was added while continuously stirring. The solution was then heated slowly to about 105 C over about thirty minutes and maintained throughout the remaining process.

Once the DNSA was completely dissolved, an approximate stoichiometric amount of ammonium nitrate was added and stirred into the solution. A potassium source such as potassium nitrate was then added in about 10-15% by weight with regard to the total amount of ammonium nitrate added. The mixture was continually stirred and the heat maintained as a solid formed. The mixing and heating is continued until the desired dryness is obtained. If desired, the mix may be formed into desired shapes such as pellets or tablets and then dried to a desired moisture content an oven for example. The resultant solid included stoichiometric amounts of phase stabilized ammonium nitrate (PSAN) and ammonium dinitrosalicylic acid (ADNSA). The resultant ADNSA crystals are comparatively small and therefore form an intimate co-precipitation with the ammonium nitrate.

Example 3

Wet Mix Method Including A Secondary Fuel

A composition was made by providing a stainless steel jacketed mixing vessel containing about two liters of water. To this solution, about 753 grams of dinitrosalicylic acid (DNSA) was added while continuously stirring. The solution was then heated slowly to about 105 C over about thirty minutes and maintained throughout the remaining process. Once the DNSA was completely dissolved, about 4352 grams of ammonium nitrate, about 122 grams of potassium nitrate, about 227 grams of potassium carbonate (whereby potassium nitrate and potassium carbonate taken together provide a potassium source for phase stabilization of the ammonium nitrate), about 595 grams of diammonium bitetrazole, and one liter of water are added together into the vessel, while continuously and mechanically stirring. A bright yellow precipitate forms immediately in a viscous, paint-like consistency. After about one hour, the mix forms crumbly solids. The mixing and heating is continued until the desired dryness is obtained. If desired, the may be formed or extruded into desired shapes such as pellets or tablets and then dried to a desired moisture content, in an oven for example.

Example 4

A composition containing about 73% ammonium nitrate and about 27 wt % monopotassium dinitrosalicylic acid was wet mixed and formed into a homogeneous composition in accordance with the present invention. The resultant composition included phase stabilized ammonium nitrate at about 75.20 wt % (the PSAN containing 64.95 of ammo nitrate and 10.25 wt % potassium nitrate) and ammonium dinitrosalicylic acid at about 24.80 wt %.

Example 5

A composition containing about 76.39 wt % phase stabilized ammonium nitrate (containing about 7.64 wt % potassium nitrate as a phase stabilizer); about 10 wt % diammonium salt of 5,5′-bis-1H-tetrazole; and about 13.61 wt % ammonium dinitrosalicylic acid was dry mixed and formed into a homogeneous composition in accordance with the present invention.

Example 6

A composition containing about 68.75 wt % ammonium nitrate; about 7.64 wt % potassium nitrate; about 10 wt % di-ammonium salt of 5.5′-bis-1H-tetrazole: and about 13.61 wt % ammonium dinitrosalicylic acid was dry mixed and formed into a homogeneous composition in accordance with the present invention.

Example 7

A composition containing about 67.58 ammonium nitrate; about 7.51 wt % potassium nitrate; about 7.0 wt % di-ammonium salt of 5,5′-bis-1H-tetrazole; about 3.0 wt % of dipotassium tartaric acid and about 14.91 w ammonium dinitrosalicylic acid was dry mixed and formed into a homogeneous composition in accordance with the present invention.

Example 8

A composition containing about 68.4 wt % ammonium nitrate; about 7.6 wt % potassium nitrate; about 5 wt % di-ammonium salt of 5,5′-bis-1H-tetrazole; and about 20.5 wt % ammonium dinitrosalicylic acid was mixed and formed into a homogeneous composition in accordance with the present invention.

Example 9

Comparative Example (PSAN-Tetrazole)

A composition containing about 73.5 wt % phase stabilized ammonium nitrate and about 26.5 wt % ammonium salt of 5,5′-bis-tetrazole amine was dry mixed and formed into a homogeneous composition in accordance with methods known in the art.

Example 10

Comparative Example (PSAN-Tetrazole)

A composition/gas generant formed as provided in Example 9 was evaluated based on gaseous effluent. A given mass of the composition contained about 3.9% carbon and when combusted in a single-stage one mole inflator (that is containing one mole of gas generant and operating at about 33-35 MPa), the parts per million of the following gaseous products were measured from a 100 cubic foot tank: 126 ppm carbon monoxide; 41 ppm ammonia; 13 ppm nitrogen oxide; and 0 ppm nitrogen dioxide. The same mass of the same fuel was also combusted in a double stage one mole inflator (that is containing one mole of gas generant and operating at about 40 MPa), and resulted in the following gaseous products as also measured from a 100 cubic foot tank: 129 ppm carbon monoxide; 35 ppm ammonia; 11 ppm nitrogen oxide; and 0 ppm nitrogen dioxide.

Example 11

A composition/gas generant formed as provided in Example 4 was evaluated based on gaseous effluent. A given mass of the composition contained about 8.5% carbon and when combusted in a single-stage one mole inflator (the same model inflator as used in Example 10, and one that contained one mole of gas generant and operated at about 33-35 MPa), the parts per million of the following gaseous products were measured from a 100 cubic foot tank: 173 ppm carbon monoxide; 14 ppm ammonia; 12 ppm nitrogen oxide; and 0 ppm nitrogen dioxide. In accordance with the present invention, the results illustrate that although this example had more than twice the amount of carbon content in the gas generant composition as compared to Example 10, there was only about a 37% increase in the amount carbon monoxide produced upon combustion. Furthermore, the ammonia content was about one third or about 33% of the amount of ammonia produced in the composition Example 10. The results were unexpected and counterintuitive in that the expectation had been to see, a linear and increased amount of carbon monoxide produced upon combustion. Instead, useful amounts of carbon dioxide and nitrogen were produced while attenuating the production of carbon monoxide as analyzed from the pre-combustion content of carbon in the gas generant. Accordingly, the present invention supplants less desirable gases such as ammonia with acceptable gases such as carbon dioxide, while surprisingly mitigating the production of carbon monoxide.

Example 12

A composition/gas generant formed as provided in Example 4 was evaluated based on gaseous effluent. A given mass of the composition contained about 6.0% carbon and when combusted in a single-stage one mole inflator (the same model inflator as used in Example 10, and one that contained one mole of gas generant and operated at about 33-35 MPa), the parts per million of the following gaseous products were measured from a 100 cubic foot tank: 122 ppm carbon monoxide; 11 ppm ammonia; 20 ppm nitrogen oxide; and 0 ppm nitrogen dioxide. In accordance with the present invention, the results illustrate that although this example had more than 150% if the amount of carbon content in the gas generant composition a compared to Example 10, there was less carbon monoxide (96.8% as compared to Example 10) produced upon combustion. Furthermore, the ammonia content was about 268% of the amount of ammonia produced in the composition of Example 10. The results were unexpected and counterintuitive in that the expectation had been to see a linear amount of carbon monoxide produced upon combustion. Instead, useful amounts of carbon dioxide and nitrogen were produced while attenuating the production of carbon monoxide as analyzed from the pre-combustion content of carbon in the gas generant. Accordingly, the present invention supplants less desirable gases such as ammonia with acceptable gases such as carbon dioxide, while surprisingly mitigatin the production of carbon monoxide.

The same mass of the same fuel as also combusted in a double stage one mole inflator (the same model inflator as used in Example 10 and one that contained one mole gas generant and operated at about 40 MPa), and resulted in the following gaseous products as also measured from a 100 cubic foot tank: 135 ppm carbon monoxide: 14 ppm ammonia; 12 ppm nitrogen oxide; and 0 ppm nitrogen dioxide. Again, the present invention supplants less desirable gases such as ammonia with acceptable gases such as carbon dioxide, while surprisingly mitigating the production of carbon monoxide.

Example 13

Comparative Example (PSAN-Tetrazole)

A composition/gas generant formed as in Example 10 was combusted within a single stage one mole inflator as employed in Example 10. The peak inflator chamber pressure attained in sustained combustion was about 37 MPa at about 0.015 seconds after combustion began. Gas outputs within a 60-liter ballistic tank were measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began, and then leveled off at a sustained pressure of about 31-32 MPa through 0.1 seconds after combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressure utilized in vehicle occupant protection systems.

Example 14

A composition/gas generant formed in accordance with the present invention and as described in Example 4, was combusted within a single stage one mole inflator as employed in Example 10. the peak inflator chamber pressure attained in sustained combustion was about 32 MPa at about 0.013 seconds after combustion began. Gas outputs within a 60-liter ballistic tank were measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began, and then leveled off at a sustained pressure of about 28-31 MPa through 0.1 seconds after combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressure utilized in vehicle occupant protection systems. Quite unexpectedly, it has been discovered that compositions provided in accordance with the present invention operate at a peak inflator pressure that is 5 MPa lower than the inflator of Example 13, and yet provide substantially equivalent amounts of sustained pressure in the ballistic tank. Accordingly, it can be seen that the present compositions can sustainably combust at a lower inflator pressure thereby relaxing the structural requirements of the inflator while yet providing similar performance from the standpoint of gas generation over time.

Example 15

A composition/gas generant formed in accordance with the present invention and as described in Example 4, was combusted within a single stage one mole inflator similar or equivalent to the one employed in Example 10. The peak inflator chamber pressure attained in sustained combustion was about 26 MPa at about 0.015 seconds after combustion began. Gas outputs within a 60-liter ballistic tank were measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began, and then leveled off at a sustained pressure of about 30-28 MPa through 0.1 seconds after combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressure utilized in vehicle occupant protection systems. Quite unexpectedly, it has been discovered that compositions provided in accordance with the present invention operate at a peak inflator pressure that is about 11 MPa lo than the inflator of Example 13, and yet provide substantially equivalent amounts of sustained pressure in the ballistic tank. Accordingly, it can be seen that the present compositions can sustainably combust at a lower inflator pressure thereby relaxing the requirements of the inflator while yet providing similar performance from the standpoint of gas generation over time.

Example 16

A composition/gas generant formed in accordance with the present invention and as described in Example 4, was combusted within a single stage one mole inflator similar or equivalent to the one employed in Example 10. The peak inflator chamber pressure attained in sustained combustion was about 22.5 MPa at about 0.013 seconds after combustion began. Gas outputs a 60-liter ballistic to ere measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began, and then leveled off at a sustained pressure of about 30-28 Pa through 0.1 seconds after combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressurized in vehicle occupant protection systems. Quite unexpectedly, it has been discovered that compositions provided in accordance with the present invention operate at a peak inflator pressure that is about 14.5 MPa lower than the inflator of Example 13, and yet provide substantially equivalent amounts of sustained pressure in the ballistic tank. Accordingly, it can be seen that the present compositions can sustainably combust at a lower inflator pressure thereby relaxing the structural requirements of the inflator while yet providing similar performance from the standpoint of gas generation over time.

Example 17

A composition/gas generant formed in accordance with the present invention and as described in Example 4, was combusted within a single stage one mole inflator similar or equivalent to the one employed in Example 10. The peak inflator chamber pressure attained in sustained combustion was about 20 MPa at about 0.015 seconds after combustion began. Gas outputs within a 60-liter ballistic tank were measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began and then leveled off at a sustained pressure of about 28-30 MPa through 0.1 seconds a combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressure utilized in vehicle occupant protection systems. Quite unexpectedly, it has been discovered that compositions provided in accordance with the present invention operate at a peak inflator pressure that is about 17 MPa lower than the inflator of Example 13, and yet provide substantially equivalent amounts of sustained pressure in the ballistic tank. Accordingly, it can be seen that the present compositions can sustainably combust at a lower inflator pressure thereby relaxing the structural requirements of the inflator while yet providing similar performance from the standpoint of gas generation over time.

Example 18

A composition gas generant formed in accordance with the present invention and as described in Example 4, was combusted within a single stage one mole inflator similar or equivalent to the one employed in Example 10. The peak inflator chamber pressure attained in sustained combustion was about 7.5 MPa at about 0.015 seconds after combustion began. Gas outputs within a 60-liter ballistic tank were measured from the beginning of combustion at T₀ through 0.1 seconds after combustion. The ballistic tank pressure steadily increased up through 0.05 seconds after combustion began, and then leveled off at a sustained pressure of about 28-27 MPa through 0.1 seconds after combustion began. Sustained pressure indicates suitable gas generating properties that accommodate the sustained pressure utilized in vehicle occupant protection systems. Quite unexpectedly, it has been discovered that compositions provided in accordance with the present invention operate at a peak inflator pressure that is about 19.5 MPa lower than the inflator of Example 13, and yet provide substantially equivalent amounts of sustained pressure in the ballistic tank. Accordingly, it can be seen that the present compositions can sustainably combust at a lower inflator pressure thereby relaxing the structural requirements of the inflator while yet providing similar performance from the standpoint of gas generation over time.

Example 19

A composition formed as described in Example 4 exhibited burn rates in inches per second (ips) of about: 0.64 at 1000 pounds per square inch gauge (psig); 0.82 at 2000 psig 0.98 at 2500 psig; 1.02 at 3500 psig; 1.12 at 4500 psig; and 1.22 at 5500 psig.

Example 20

Comparative Example (PSAN-Tetrazole)

A composition formed as described in Example 10 exhibited burn rates in inches per second (ips) of about: 0.48 at 1000 pounds per square inch gauge (psig); 0.82 at 2000 psig; 0.92 at 2500 psig; 1.02 at 3500 psig; 1.08 at 4500 psig; and 1.12 at 5500 psig.

When compared to Example 19, it can be seen that compositions of the present invention exhibit suitable burn rates substantially equivalent to another state-of-the-art gas generant composition as described in Example 10.

Example 21

A composition formed to contain a primary fuel of ammonium dinitrosalicylic acid at about 10-20 weight percent, a secondary fuel of diammonium salt of 5,5′-bis-1H-tetrazole at about 3-15 weight percent, and phase stabilized ammonium nitrate containing ammonium nitrate and potassium nitrate as an oxidizer with the ammonium nitrate at about 60-75 weight percent and potassium nitrate at about 5-10 weight percent.

As illustrated above, gas generating compositions of the present invention including salts of dinitrosalicylic acid combined with phase stabilized ammonium nitrate result in low combustion solids, with reduced levels of less desirable combustion gases compared to other state of-the-art gas generants while operating at reduced combustion pressures. Other benefits may include reduced manufacturing costs, improved thermal stability, improved chemical ability, and/or reduced processing costs.

As shown in FIG. 1, an exemplary inflator or generating system 10 incorporates a dual chamber design containing a primary gas generating composition 1 formed as described herein, that may be manufactured as known in the art. U.S. Pat. Nos. 6,422,601, 6,805,377, 6,659,500, 6,749,219, and 6,752,421 exemplify typical airbag inflator designs and are each incorporated herein by reference in their entirety.

Referring now to FIG. 2, the exemplary inflator or gas generating system 10 described above may also be incorporated into an airbag system 200. Airbag system 200 includes at least one airbag 202 and an inflator 10 containing a gas generant composition 12 in accordance with the present invention, coupled to airbag 202 so as to enable fluid communication with an interior of the airbag. Airbag system 200 may also include (or be in communication with) a crash event sensor 210. Crash event sensor 210 includes a known crash sensor algorithm that signals actuation of bag system 200 via, for example, activation of airbag inflator 10 in the event of a collision

Referring again to FIG. 2, airbag system 200 may also be incorporated into a broader; more comprehensive vehicle occupant restraint system 180 including additional elements such as a safety belt assembly 150. FIG. 2 shows a schematic diagram of one exemplary embodiment of such a restraint system. Safety belt assembly 150 includes a safety belt housing 152 and a safety belt 100 extending from housing 152. A safety belt or mechanism 154 (for example, a spring-loaded mechanism) may be coupled to an end portion of the belt. In addition, a safety belt pretensioner 156 containing gas generating composition 12 may be coupled to belt retractor mechanism 154 to actuate the retractor mechanism in the event of a collision. Typical seat belt retractor mechanisms which may be used in conjunction with the safety belt embodiments of the present invention are described in U.S. Pat. Nos. 5,743,480, 5,553,803, 5,667,161, 5,451,008, 4,558,832 and 4,597 546, incorporated herein by reference. Illustrative examples of typical tensioners with which the safety belt embodiments of the present invention may be combined are described in U.S. Pat. Nos. 6,505,790 and 6,419,177, incorporated herein by reference.

Safety belt assembly 150 may also include (or be in communication with) a crash event sensor 158 (for example, an inertia sensor or an accelerometer) including a known crash sensor algorithm that signals actuation of belt pretensioner 156 via, for example, activation of a pyrotechnic igniter (not shown) incorporated into the pretensioner. U.S. Pat. Nos. 6,505,790 and 6,419,177, previously incorporated herein by reference, provide illustrative examples of pretensioners actuated in such a manner.

It should be appreciated that safety belt assembly 150, airbag system 200, and re broadly, vehicle occupant protection system 180 exemplify but do not limit gas generating systems contemplated in accordance with the present invention.

It should further be understood that the preceding is merely a detailed description of various embodiments of this invention and that numerous changes to the disclosed embodiments can be made in accordance with the disclosure herein without departing from the scope of the invention. The preceding description, therefore, is not meant to the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. 

What is claimed is:
 1. A gas generating composition comprising: a fuel having a structural formula of or derived from the following structural formula:

and phase stabilized ammonium nitrate as an oxidizer.
 2. The composition of item 1 comprising a fuel selected from a metallic or nonmetallic salt of said structural formula.
 3. The composition of item 1 comprising a fuel selected from an adduct of said structure with another compound, wherein said adduct with said other compound forms a hydrogen bonded complex.
 4. The composition of item 2 wherein said metallic salt is an alkali or alkaline earth metal salt.
 5. A gas generating composition comprising: a fuel selected from 3,5-dinitrosalicylic acid, a metal or non-metal salt of 3,5 dinitrosalicylic acid, an adduct of 3,5-dinitrosalicylic acid and mixtures thereof; and an oxidizer wet mixed with said fuel, said oxidizer selected from ammonium nitrate and phase stabilized ammonium nitrate.
 6. A gas generating composition comprising: a primary fuel selected from 3,5-dinitrosalicylic acid, a metal or non-metal salt of 3,5 dinitrosalicylic acid, an adduct of 3,5-dinitrosalicylic acid, and mixtures thereof, said primary fuel provided at about 5-80 weight percent of said composition; a second fuel selected from the group consisting of tetrazoles and salts thereof; triazoles and salts thereof azoles and salts thereof guanidines and salts thereof; guanidine derivatives; imides; amides; aliphatic carboxylic acids and salts thereof; aromatic carboxylic acids and salts thereof nitro-aromatic carboxylic acids and salts thereof; nitrosalicylic acids and salts thereof; amines; nitrophenols; pyrazoles; imidazoles; azines; and mixtures thereof, said secondary fuel provided at about 0-50 weight percent of said composition; and a primary oxidizer selected from metal and nonmetal nitrates, nitrites, chlorates, perchlorates, oxides, hydroxides, basic metal nitrates, and mixtures thereof, said primary oxidizer provided at about 20-80 weight percent of said composition.
 7. The composition of claim 6 comprising an oxidizer selected from phase stabilized ammonium nitrate, ammonium nitrate, strontium nitrate, potassium nitrate, and mixtures thereof.
 8. The composition of claim 6 wherein said second fuel is selected from the group consisting of diammonium salt of 5,540 -bis-1H-tetrazole, monoammonium salt of bis tetrazole amine, and mixtures thereof.
 9. The composition of claim 6 wherein said primary fuel is selected from dinitrosalicylic acid, ammonium dinitrosalicylic acid, potassium dinitrosalicylic acid, strontium dinitrosalicylic acid, copper dinitrosalicylic acid, and mixtures thereof
 10. The composition of claim 6 wherein said primary fuel is provided at about 25-80 weight percent of said composition; said secondary fuel is provided at about 0.1-30 weight percent of said composition; and said primary oxidizer is provided at about 25-75 weight percent of said composition.
 11. The composition of claim 6 wherein said primary fuel is potassium dinitrosalicylic acid at about 27 weight percent of said composition, and ammonium nitrate at about 73 weight percent of said composition.
 12. The composition of claim 6 wherein said primary fuel is ammonium dinitrosalicylic acid at about 10-20 weight percent, said secondary fuel is diammonium salt of 5,5′-bis-1H-tetrazole at about 3-15 weight percent, and said oxidizer is ammonium nitrate at about 60-75 weight percent and potassium nitrate at about 5-10 weight percent. 